Cosmetic compositions using polyether siloxane copolymer network compositions

ABSTRACT

A composition comprising the reaction products of 
 
M a M H   b M E   c D d D H   e D E   f T g T H   h T E   i Q j  
where  
     M=R 1 R 2 R 3 SiO 1/2 ;  
     M H =R 4 R 5 H SiO 1/2 ;  
     M E =R 6 R 7 R E SiO 1/2 ;  
     D=R 8 R 9 SiO 2/2 ;  
     D H =R 10 HSiO 2/2 ;  
     D E =R 11 R E SiO 2/2 ;  
     T=R 12 SiO 3/2 ;  
     T H =HSiO 3/2 ;  
     T E =R E SiO 3/2 ; and  
     Q=SiO 4/2 ;  
     where R 1 , R 2 , R 3 , R 8 , R 9  and R 12  are independently monovalent hydrocarbon radicals having from one to sixty carbon atoms; R 4 , R 5  and R 10  are independently monovalent hydrocarbon radicals having from one to sixty carbon atoms or hydrogen; R 6 , R 7 , R 11  are independently monovalent hydrocarbon radicals having from one to sixty carbon atoms or R E ; each R E  is independently a monovalent hydrocarbon radical containing one or more oxirane moieties having from one to sixty carbon atoms; the stoichiometric subscripts a, b, c, d, e, f, g, h, i, and j are either zero or positive subject to the following limitations: a+b+c&gt;1; b+e+h&gt;1; c+f+i&gt;1; b+e+h&gt;c+f+i. In a preferred embodiment the reaction product of the present invention is a polyether siloxane copolymer network. In another preferred embodiment embodiment the reaction product of the present invention is a polyether siloxane copolymer network swollen with a volatile low molecular weight silicon containing compound. These compositions are useful for a variety of personal care compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation-in-Part Application of U.S.Ser. No. 10/922,487 filed Aug. 20, 2004 which is a ContinuationApplication of U.S. Ser. No. 10/439,857 filed May 16, 2003 which is aContinuation-In-Part Application of U.S. Ser. No. 10/393,858 filed Mar.21, 2003, now U.S. Pat. No. 6,759,479 which is a Continuation-In-PartApplication of U.S. Ser. No. 09/858,795 filed May 16, 2001 now U.S. Pat.No. 6,538,061.

FIELD OF THE INVENTION

The present invention relates to silicone compositions, moreparticularly to compositions comprising a silicone polymer networkcomprising cross-links derived from epoxide or oxirane moieites.

BACKGROUND OF THE INVENTION

The personal care industry thrives on being able to deliver multipleperformance products based on mixtures of several components, with eachhaving performance characteristics important to or desirable in thefinal formulation. One desirable characteristic is the ability toprovide a silky initial feel derived from low molecular weightsilicones, such as for example, octamethylcyclotetrasilioxane ordecamethylcyclopentasiloxane, in the formulation while maintaining ahigh, but shear-thinnable viscosity. While these low molecular weightsilicones provide the desired feel characteristics, they are also lowviscosity, highly flowable liquids. Thus they are not easily held in aformulation, preferring rather to separate and flow out of a givencontainer or flow uncontrollably across the skin when used in a specificapplication. Further, it desirable to achieve an initial silky feelwhile providing a smooth, low-residue feel upon dry-down. Polymericsilicone gels prepared in volatile silicone have been found to deliverdesirable initial feel of volatile, low viscosity silicones toformulations while at the same time provide high viscosity and a smoothsilky feel on dry-down, see for example, U.S. Pat. Nos. 5,760,116,5,493,041 and 4,987,169.

Such polymeric silicone gels have typically been made by thehydrosilylation reaction, which requires the use of both SiH functionalgroups and terminal olefinic groups to form crosslinked siloxanepolymers. Thus only siloxane structures that can incorporatesilylhydride groups and optionally, vinyl functional siloxane groups,can be utilized in making these materials. Further this method ofgenerating crosslinked siloxane polymers limits the range of desirableorganofunctional groups that may be incorporated into the polymericstructure to create additional performance advantages in complexformulations. Thus attempts to include organofunctional groups into thecrosslinked siloxane polymer include unsaturated organic groupscompatible with the hydrosilylaton reaction.

SUMMARY OF THE INVENTION

A cosmetic composition comprising the reaction products ofM^(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E)_(i)Q_(j)where

M=R¹R²R³SiO_(1/2);

M^(H)=R⁴R⁵H SiO_(1/2);

M^(E)=R⁶R⁷R^(E)SiO_(1/2);

D=R⁸R⁹SiO_(2/2);

D^(H)=R¹⁰HSiO_(2/2);

D^(E)=R¹¹R^(E)SiO_(2/2);

T=R¹²SiO_(3/2);

T^(H)=HSiO_(3/2);

T^(E)=R^(E)SiO_(3/2); and

Q=SiO_(4/2);

where R¹, R², R³, R⁸, R⁹ and R¹² are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms; R⁴, R⁵ andR¹⁰ are independently monovalent hydrocarbon radicals having from one tosixty carbon atoms or hydrogen; R⁶, R⁷, R¹¹ are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms or R^(E);each R^(E) is independently a monovalent hydrocarbon radical containingone or more oxirane moieties having from one to sixty carbon atoms; thestoichiometric subscripts a, b, c, d, e, f, g, h, i, and j are eitherzero or positive subject to the following limitations:a+b+c>1; b+e+h>1;c+f+i>1; b+e+h>c+f+i; and when d+e+f+g+h+i+j=0, a+b+c=2. In a preferredembodiment the reaction product of the present invention is a polyethersiloxane copolymer network. In another preferred embodiment the reactionproduct of the present invention is a polyether siloxane copolymernetwork swollen with a volatile low molecular weight silicon containingcompound. These compositions are useful for a variety of personal carecompositions.

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention comprise the reaction productsof an epoxy functional hydrido siloxane molecule having the followingformula:M_(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E)_(i)Q_(j)where

M=R¹R²R³SiO_(1/2);

M^(H)=R⁴R⁵H SiO_(1/2);

M^(E)=R⁶R⁷R^(E)SiO_(1/2);

D=R⁸R⁹SiO_(2/2);

D^(H)=R¹⁰HSiO_(2/2);

D^(E)=R¹¹R^(E)SiO_(2/2);

T=R¹²SiO_(3/2);

T^(H)=HSiO_(3/2);

T^(E)=R^(E)SiO_(3/2); and

Q=SiO_(4/2);

where R¹, R², R³, R⁸, R⁹ and R¹² are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms; R⁴, R⁵ andR¹⁰ are independently monovalent hydrocarbon radicals having from one tosixty carbon atoms or hydrogen; R⁶, R⁷, R¹¹ are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms or R^(E);each R^(E) is independently a monovalent hydrocarbon radical containingone or more oxirane moieties having from one to sixty carbon atoms; thestoichiometric subscripts a, b, c, d, e, f, g, h, i, and j are eitherzero or positive subject to the following limitations: a+b+c>1; b+e+h>1;c+f+i>1; b+e+h>c+f+i; and when d+e+f+g+h+i+j=0, a+b+c=2.

One method of producing the composition of the present invention is toreact a molecule having the following formula:M_(a)M^(H) _(b′)D_(d)D^(H) _(e′)T_(g)T^(H) _(h′)Q_(j)wherein the definitions and relationships are as later defined (and alsoconsistent with those defined above) under hydrosilylation conditionswith an olefinically unsaturated molecule containing one or more oxiranemoieties under conditions of stoichiometry where the molar quantity ofoxirane is less than the molar quantity of silyl hydride. As used hereinthe phrase “an olefinically unsaturated molecule containing one or moreoxirane moieties” means a molecule possessing one or more interior,pendant or terminal carbon carbon double bonds simultaneously with oneor more interior, pendant or terminal three membered oxygen containingheterocyclic rings (chemically the phrase “three membered oxygencontaining heterocyclic ring” is used herein interchangeably with theoxirane or epoxide structures). The simplest chemical structureexemplified by such a definition is:

but also includes alicyclic structures exemplified by:

where the subscript k may be zero or a positive integer, more preferablya positive integer ranging generally from 0 to about 10. It should benoted that both exemplified structures are terminal in both the olefinicmoiety and the oxirane (epoxide) moiety. A more general chemicalstructure is:

where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently selectedfrom the group of hydrogen and monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms, Q_(m) is a di- or trivalent hydrocarbonradical having from one to sixty carbon atoms, Q_(n) is a divalenthydrocarbon radical having from one to sixty carbon atoms with thesubscripts m and n independently zero or one subject to the limitationthat when Qm is trivalent one of R¹³ or R¹⁴ is absent and where R¹⁶ andR¹⁸ may be either cis- or trans- to each other.

Thus one possible synthetic pathway to prepare the reaction products ofthe present invention is as follows:M_(a)M^(H) _(b′)D_(d)D^(H) _(e′)T_(g)T^(H) _(h′)Q_(j)+α

reacting under hydrosilylation conditions to yield M_(a)M^(H) _(b)M^(E)_(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E) _(i)Q_(j) when thestoichiometric coefficient, α, is less than the sum of b′+e′+h′. Itshould be noted that the stoichiometric coefficients b, e, and h definethe quantity of hydride bearing species M^(H), D^(H) and T^(H) in bothreactant and product and are related one to other in that fashion butbecause some of the hydride bearing functions have reacted with anolefinically unsaturated molecule containing one or more oxiranemoieties the following relationships must necessarily obtain:b′+e′+h′>b+e+h and b+c+e+f+h+i=b′+e′+h′. It is to be noted thatacetylene analogs of the olefinically unsaturated oxirane containingmolecules will produce similar species that will react to form similarproducts. Thus as used herein the phrase an olefinically unsaturatedmolecule containing one or more oxirane moieties is intended to alsoinclude an acetylenically unsaturated molecule containing one or moreoxirane moieties. The phrase “an acetylenically

unsaturated molecule containing one or more oxirane moieties” means amolecule possessing one or more interior, pendant or terminal carboncarbon triple bonds simultaneously with one or more interior, pendant orterminal three membered oxygen containing heterocyclic rings (chemicallythe phrase “three membered oxygen containing heterocyclic ring” is usedherein interchangeably with the oxirane or epoxide structures). When theepoxide compound is an olefinic epoxide, a specific example being:then R^(E) as a substituent, becomes

with all the definitions consistent with those as previously defined.When the epoxide is an acetylenic epoxide, a specific example being:

then R^(E) as a substituent, becomes either:

with all the definitions consistent with those as previously defined.

The silyl hydride bearing precursor molecule, M^(a)M^(H) _(b′)D_(d)D^(H)_(e′)T_(g)T^(H) _(h′)Q_(j), can be prepared by a variety of techniquesknown in the art. Epoxy substituted siloxanes are prepared in the normalmanner through the use of a hydrosilylation reaction to attach a vinylor allyl substituted epoxide onto an SiH bearing siloxane. SiHcontaining siloxanes are well known in the art and can be linear,branched, or cyclic in structure. Examples of useful vinyl or allylsubstituted epoxides include 4-vinyl cyclohexene oxide, allyl glycidylether, limonene oxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene,norbornadiene monoepoxide and 1,2-epoxy-9-decene. Precious metalcatalysts suitable for making epoxy siloxanes are also well known in theart and comprise complexes of rhodium, ruthenium, palladium, osmium,iridium and/or platinum.

Many types of platinum catalysts for this SiH olefin addition reaction(hydrosilation or hydrosilylation) are known and such platinum catalystsmay be used for the reaction in the present instance. When opticalclarity is required the preferred platinum catalysts are those platinumcompound catalysts that are soluble in the reaction mixture. Theplatinum compound can be selected from those having the formula(PtCl₂Olefin) and H(PtCl₃Olefin) as described in U.S. Pat. No.3,159,601, hereby incorporated by reference. A further platinumcontaining material usable in the compositions of the present inventionis the cyclopropane complex of platinum chloride described in U.S. Pat.No. 3,159,662 hereby incorporated by reference. Further the platinumcontaining material can be a complex formed from chloroplatinic acidwith up to 2 moles per gram of platinum of a member selected from theclass consisting of alcohols, ethers, aldehydes and mixtures of theabove as described in U.S. Pat. No. 3,220,972 hereby incorporated byreference. The catalysts preferred for use are described in U.S. Pat.Nos. 3,715,334; 3,775,452; and 3,814,730 to Karstedt. Additionalbackground concerning the art may be found at J. L. Spier, “HomogeneousCatalysis of Hydrosilation by Transition Metals, in Advances inOrganometallic Chemistry, volume 17, pages 407 through 447, F. G. A.Stone and R. West editors, published by the Academic Press (New York,1979). Persons skilled in the art can easily determine an effectiveamount of platinum catalyst. Generally, an effective amount ranges fromabout 0.1 to 50 parts per million of the total organopolysiloxanecomposition.

The reaction product of M_(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E)_(f)T_(g)T^(H) _(h)T^(E) _(i)Q_(j) produces a polymer network, believedto be a polyether siloxane copolymer network (or alternatively asiloxane polyether copolymer network). As used herein, the terminology“network” means a three dimensionally extending structure comprisinginterconnected polyether siloxane copolymer chains. Preferably, fluid iscontained within interstices of the network. The term “interstices” isused herein in reference to a network to denote spaces within thenetwork, that is, spaces between the polyether siloxane copolymer chainsof the network. As used herein in the context of the polyether siloxanecopolymer network, the term polyether is intended to include thereaction product of two or more epoxide moieties to form one or moreether linkages that form a cross link between siloxane chains ormoieties.

In one preferred embodiment, the polyether siloxane copolymer network isa crosslinked network that is insoluble in the fluid component of thesilicone composition of the present invention, but that is capable ofbeing swollen by the fluid. The amount of crosslinking present in thecrosslinked network may be characterized with respect to the degree ofswelling exhibited by the network in the fluid. In another preferredembodiment, the crosslinked structure of the network is effective toallow the network to be swollen by a low molecular weight fluid orsilicone fluid, such as, for example, decamethylcyclopentasiloxane, fromits original volume to a swollen volume that is a factor of from 1.01 to5000, more preferably from 2 to 1000, and even more preferably from 5 to500, times its original volume. The original volume of the network canbe determined, for example, by extracting or evaporating all of thefluid component from the silicone composition of the present inventionto leave the original volume, that is, the volume of the polyethersiloxane copolymer network in the absence of the fluid.

As used herein the terminology “hydrocarbon radical” includes acyclichydrocarbon radicals, alicyclic hydrocarbon radicals and aromatichydrocarbon radicals.

As used herein in reference to a hydrocarbon radical, the term“monovalent” means that the radical is capable of forming one covalentbond per radical, the term “divalent” means that the radical is capableof forming two covalent bonds per radical and the term “trivalent” meansthat the radical is capable of forming three covalent bonds per radical.Generally, a monovalent radical can be represented as having beenderived from a saturated hydrocarbon compound by conceptual removal ofone hydrogen atom from the compound, a divalent radical can berepresented as having been derived from a saturated hydrocarbon compoundby conceptual removal of two hydrogen atoms from the compound and atrivalent radical can be represented as having been derived from asaturated hydrocarbon compound by conceptual removal of three hydrogenatoms from the compound. For example, an ethyl radical, that is,a-CH₂CH₃ radical, is a monovalent radical; a dimethylene radical, thatis, a-(CH₂)₂—radical, is a divalent radical and an ethanetriyl radical,that is,

radical, is a trivalent radical, each of which can be represented ashaving been derived by conceptual removal of one or more hydrogen atomsfrom the saturated hydrocarbon ethane.

As used herein, the terminology “acyclic hydrocarbon radical” means astraight chain or branched hydrocarbon radical, preferably containingfrom 1 to 60 carbon atoms per radical, which may be saturated orunsaturated and which may be optionally substituted or interrupted withone or more atoms or functional groups, such as, for example, carboxyl,cyano, hydroxy, halo and oxy. As long as these functional groups do notinterfere with the cationic cure mechanism of the epoxide or oxiranemoiety, suitable monovalent acyclic hydrocarbon radicals may include,for example, alkyl, alkenyl, alkynyl, hydroxyalkyl, cyanoalkyl,carboxyalkyl, alkyloxy, oxaalkyl, alkylcarbonyloxaalkylene, carboxamideand haloalkyl, such as, for example, methyl, ethyl, sec-butyl,tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl, propenyl,butynyl, hydroxypropyl, cyanoethyl, butoxy, 2,5,8-trioxadecanyl,carboxymethyl, chloromethyl and 3,3,3-fluoropropyl. Suitable divalentacyclic hydrocarbon radicals include, for example, linear or branchedalkylene radicals, such as, for example, methylene, dimethylene,trimethylene, decamethylene, ethylethylene, 2-methyltrimethylene,2,2-dimethyltrimethylene and linear or branched oxalkylene radicals suchas, for example, methyleneoxypropylene. Suitable trivalent acyclichydrocarbon radicals include, for example, alkanetriyl radicals, suchas, for example, 1,1,2-ethanetriyl, 1,2,4-butanetriyl,1,2,8-octanetriyl, 1,2,4-cyclohexanetriyl and oxaalkanetriyl radicalssuch as, for example, 1,2,6-triyl-4-oxahexane.

As used herein the term “alkyl” means a saturated straight or branchedmonovalent hydrocarbon radical. In a preferred embodiment, monovalentalkyl groups are selected from linear or branched alkyl groupscontaining from 1 to 60 carbons per group, such as, for example, methyl,ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,pentyl, hexyl, heptyl, decyl, dodecyl.

As used herein the term “alkenyl” means a straight or branchedmonovalent terminally unsaturated hydrocarbon radical, preferablycontaining from 2 to 10 carbon atoms per radical, such as, for example,ethenyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl and ethenylphenyl.

As used herein, the terminology “alicyclic hydrocarbon radical” means aradical containing one or more saturated hydrocarbon rings, preferablycontaining from 4 to 12 carbon atoms per ring, per radical which mayoptionally be substituted on one or more of the rings with one or morealkyl radicals, each preferably containing from 2 to 6 carbon atoms peralkyl radical, halo radicals or other functional groups and which, inthe case of a monovalent alicyclic hydrocarbon radical containing two ormore rings, may be fused rings. Suitable monovalent alicyclichydrocarbon radicals include, for example, cyclohexyl and cyclooctyl.Suitable divalent hydrocarbon radicals include, saturated or unsaturateddivalent monocyclic hydrocarbon radicals, such as, for example,1,4-cyclohexylene. Suitable trivalent alicyclic hydrocarbon radicalsinclude, for example, cycloalkanetriyl radicals such as, for example,1-dimethylene-2,4-cyclohexylene,1-methylethylene-3-methyl-3,4-cyclohexylene.

As used herein, the terminology “aromatic hydrocarbon radical” means ahydrocarbon radical containing one or more aromatic rings per radical,which may, optionally, be substituted on the aromatic rings with one ormore alkyl radicals, each preferably containing from 2 to 6 carbon atomsper alkyl radical, halo radicals or other functional groups and which,in the case of a monovalent aromatic hydrocarbon radical containing twoor more rings, may be fused rings. Suitable monovalent aromatichydrocarbon radicals include, for example, phenyl, tolyl,2,4,6-trimethylphenyl, 1,2-isopropylmethylphenyl, 1-pentalenyl,naphthyl, anthryl, eugenol and allylphenol as well as aralkyl radicalssuch as, for example, 2-phenylethyl. Suitable divalent aromatichydrocarbon radicals include, for example, divalent monocyclic arenessuch as, for example, 1,2-phenylene, 1,4-phenylene,4-methyl-1,2-phenylene, phenylmethylene. Suitable trivalent aromatichydrocarbon radicals include, for example, trivalent monocyclic arenessuch as, for example, 1-trimethylene-3,5-phenylene.

In a preferred embodiment, the epoxy functional organosiloxane compoundis reacted by polymerizing the epoxy functional organosiloxane compoundunder cationic polymerization conditions and, preferably, in thepresence of a fluid, preferably a volatile siloxane fluid. In oneembodiment, the epoxy functional organosiloxane compound is polymerizedin the presence of a fluid to directly form the silicone composition ofthe present invention. In another embodiment, the epoxy functionalorganosiloxane compound is polymerized in the presence of a first fluidor fluid mixture to form a polyether siloxane copolymer network, andthen the network so formed is subsequently swollen with a second fluidor fluid mixture to form the silicone composition of the presentinvention. The second fluid or fluid mixture may be the same as ordifferent from the first fluid mixture. The first solvent may,optionally, be removed from the polymerized network by, for example,evaporation, prior to addition of the second fluid. As a furtheralternative, the epoxy functional organosiloxane compound is polymerizedin the absence of a fluid to form a polyether siloxane copolymer networkand the network is subsequently swollen with a fluid or mixture offluids to form the silicone composition of the present invention. Inanother embodiment, the polymerization of the epoxy functionalorganosiloxane is conducted with a sufficient amount of excesshydridosiloxane functionality such that there is residual hydrideremaining after polymerization that may be subsequently reacted underconditions suitable for hydrosilylation with one or more alkenylfunctional compounds. This is especially advantageous in cases where thealkenyl functional compounds can act as inhibitors of cationic cure.Such alkenyl compounds are those that contain a functionality that canact as an inhibitor of the cationic cure mechanism, e.g. a base. Inanother embodiment, a small amount of a concentrated hydridosiloxane orhydridosilane compound is added in order to increase the rate ofpolymerization.

Cationic polymerization conditions can be generated by addition of anacid catalyst capable of polymerizing an epoxy group such as, forexample, by addition of onium salt generated acids and certain metalsalts, such as, for example, aluminum trichloride and ferric chloride,which act as Lewis acids or by addition of lanthanide triflates, see PCTInt. Appl. WO 0008,087. Acid catalyzed polymerization of epoxides is awell known method of forming organic polymers and has been applied toepoxy-functional siloxane compounds in order to form siloxanepolyalkyleneoxide block copolymers for use in a variety of applicationsas, for example, release coatings on paper, see, for example, U.S. Pat.No. 4,279,717, and in conjunction with organic materials to formcoatings and modified plastic compositions, see for example, U.S. Pat.Nos. 5,354,796 and 5,663,752. One precautionary note must be observed,that is if the cationic polymerization is conducted in the presence ofcyclic siloxanes, e.g. D₃, D₄ or D₅ and the like, the strength of theacid catalysis employed must be such that cationic polymerization of theepoxide moiety occurs but polymerization of the cyclic siloxane does notoccur to any appreciable extent.

In a preferred embodiment, the epoxy functional organosiloxane compoundis polymerized under cationic cure conditions generated through theinteraction with platinum and an SiH-containing compound. This epoxidepolymerization reaction route is described in U.S. Pat. No. 5,128,431and by J. V. Crivello and N. Fan, J. Polymer Sci., Part A: PolymerChemistry, pp. 1853-1863 (1997). In this embodiment, the reactionkinetics appear to be dependent upon the presence of trace quantities ofmolecular oxygen.

The polyether siloxane copolymer network compositions of the presentinvention produce a cross linked structure that possesses a certainamount of steric hindrance by reason of the cross links. This sterichindrance tends to prevent the reaction from going to completion even atlong reaction times and thus a certain amount of residual functionalitymay remain. This residual functionality provides the ability toincorporate other functionality into the polyether siloxane copolymernetwork by reaction with functionalized molecules that are not assterically constrained as the polyether siloxane copolymer network or itmust be chemically inactivated. One reason the residual functionalitymight desirably be chemically inactivated is that in the processing ofthese materials as a polyether siloxane copolymer network swollen with alow molecular weight siloxane compound (or alternatively, low molecularweight silicone fluid), usually D₃, D₄, D₅, D₆ or M′D′_(q)T′_(s)M′ aslater defined, is that processing under conditions of high shear tendsto disrupt the network reducing the level of steric hindrance and thuscould enable further cross linking reactions to occur because of thechemically exposed residual functionality. Post-cure cross linking isknown to occur in addition polymerized silicones where the additionpolymerization occurs via hydrosilylation. These materials are preparedby first hydrosilylation of a silyl hydride with an olefinic oracetylenic oxirane or epoxide compound. Thus a noble metalhydrosilylation catalyst will be present in the reaction mixture orwithin the interstices of the polyether siloxane copolymer network. Thiscatalyst may be used to further polymerize the oxirane or epoxide moiety(moieties) incorporated in the reaction product producing the polyethersiloxane copolymer network(s) of the present invention. The residualfunctionality remaining by design, i.e. by use of sub-stoichiometricquantities, or by reason of steric inhibition of reaction completion maybe further reacted as taught herein or neutralized or inhibited. U.S.Pat. Nos. 5,977,280 and 5,929,164, both herein incorporated byreference, teach such neutralization of hydrosilylation catalysts bytreatment with strong noble metal complexing ligands, for examplephosphines, amines and organic sulfur compounds such as organic sulfidesand thiols. However, some of these strongly complexing ligands, whiledeactivating a noble metal hydrosilylation catalyst are toxic and thustheir use must be avoided in some applications, e.g. personal careapplications. Thus sulfur containing amino acid esters are strong noblemetal complexing ligands and methionine methyl ester, methionine ethylester, cysteine methyl ester, cysteine ethyl ester and cysteine dimethylester have been preferred for such noble metal deactivation. It shouldbe noted that naturally occuring proteins containing disulfide linkagesthat are easily disrupted may also be used to deactivate the noble metalcatalysts employed, e.g. egg yolks and the like. Sulfur containing aminoacid amides, polypeptides and the like may also function similarly todeactivate noble metal hydrosilylation catalysts.

The method of polymer synthesis provides for incorporation of a widerange of organofunctional groups into the copolymeric structure. Thus,the inclusion of other organofunctional groups, such as, for example,organic epoxides, epoxysiloxanes, terminally unsaturated organic andalkenylsiloxane compounds can be used to modify the resultingcopolymers.

In an alternative embodiment, the organofunctional groups are introducedto the network during polymerization of the epoxyfunctionalorganosiloxane by including organofunctional compounds to the reactionmixture which are copolymerizable with the epoxy functionalorganosiloxane under the chosen polymerization reaction conditions.

In one embodiment, polymerization of the epoxy functional organosiloxaneis conducted in the presence of one or more organic epoxide compoundswhich are copolymerizable with epoxy functional hydrido siloxanes underthe polymerization conditions to form mixed polyalkyleneoxide units. Theadditional organic epoxide compounds may contain different substituentsto further modify the resulting copolymer. Suitable organic epoxidecompounds include, for example, ethylene oxide, propylene oxide,butylene oxide, cyclohexene oxide, glycidol and epoxide oils such as forexample epoxidized soybean oil.

In another embodiment, the polymerization of the epoxy functionalorganosiloxane is conducted in the presence of one or more hydroxylfunctional compounds which are copolymerizable with epoxy functionalhydrido siloxanes under the polymerization conditions to modify theproduct copolymer. Suitable hydroxyl functional compounds include, forexample, water, hydroxy-stopped polyethers, organic alcohols, includingorganic diols, carbinol functional siloxanes and hydroxy functionalorganopolysiloxane polymers, including polyethersiloxane copolymers.

In another embodiment, the polymerization of the epoxy functionalorganosiloxane is conducted in the presence one or more alkenylfunctional compounds which are copolymerizable with epoxy functionalhydrido siloxanes under the polymerization conditions to modify theproduct copolymer. Suitable alkenyl functional compounds include alkenylfunctional organic compounds, such as, for example, hexadiene, andalkenyl functional silicone compounds, such as for example, vinylpolydimethylsiloxanes. For example, an alkenyl-functional compound mayconveniently be added via hydrosilylation in those embodiments in whichthe cationic reaction conditions for reacting the epoxide groups aregenerated using platinum and a hydrido-substituted siloxane, asdescribed above.

The silicone composition may be further processed under low to highshear to adjust the viscosity and sensory feel of the composition. Thismay be achieved, for example, by subjecting the composition to amoderate to high shearing force. High shear may be applied using, forexample, a Sonolator apparatus, a Gaulin Homogenizer or a MicroFluidizer apparatus. Optionally, one or more fluids may be added to thesilicone composition prior to the shearing.

In a preferred embodiment, the silicone composition of the presentinvention is a solid, typically having a creamy consistency, wherein thecopolymer network acts as a means for gelling the fluid to reversiblyimpart characteristics of a solid to the fluid. At rest, the siliconecomposition exhibits the properties of a solid gel material. Thesilicone composition of the present invention exhibits high stabilityand resistance to syneresis, that is, the composition exhibits little orno tendency for fluid to flow from the composition and imparts highstability and syneresis resistance to personal care compositions whichinclude the silicone composition as a component. The high stability andsyneresis resistance persists with prolonged aging of such siliconecompositions and personal care compositions. However, fluid may bereleased from the network by subjecting the silicone composition to ashearing force, such as, for example, by rubbing the composition betweenone's fingers, to provide improved sensory feel characteristic of thefluid component of the silicone material.

Fluids suitable for use as the fluid component of the composition of thepresent invention are those compounds or mixtures of two or morecompounds that are in the liquid state at or near room temperature, forexample, from about 20° C. about 50° C., and about one atmospherepressure, and include, for example, silicone fluids, hydrocarbon fluids,esters, alcohols, fatty alcohols, glycols and organic oils. In apreferred embodiment, the fluid component of the composition of thepresent invention exhibits a viscosity of below about 1,000 cSt,preferably below about 500 cSt, more preferably below about 250 cSt, andmost preferably below 100 cSt, at 25° C.

In a preferred embodiment, the fluid component of the present inventioncomprises an emollient compound. Suitable emollient compound include anyfluid that provides emollient properties, that is, that when applied toskin, tend to remain on the surface of the skin or in the stratumcorneum layer of the skin to act as lubricants, reduce flaking and toimprove the appearance of the skin. Emollient compound are genericallyknown and include, for example, hydrocarbons, such as for example,isododecane, isohexadecane and hydrogenated polyisobutene, organicwaxes, such as for example, jojoba, silicone fluids, such as, forexample, cyclopentasiloxane, dimethicone and bis-phenylpropyldimethicone, esters, such as, for example, octyldodecyl neopentanoateand oleyl oleate, as well as fatty acids and alcohols, such as forexample, oleyl alcohol and isomyristyl alcohol.

In a highly preferred embodiment, the fluid component of the presentinvention comprises a silicone fluid, more preferably a silicone fluidthat exhibits emollient properties, preferably a low molecular weightsilicone fluid or alternatively a low molecular weight siloxanecompound. Suitable silicone fluids include, for example, cyclicsilicones of the formula D_(r), wherein D, R⁸ and R⁹ are as previouslydefined, preferably with R⁸ and R⁹ chosen from the group consisting ofmonovalent one to six carbon atom monovalent hydrocarbon radicals, morepreferably methyl, and r is an integer wherein 3≦r≦12, such as, forexample, hexamethylcyclotrisiloxane (“D₃”), octamethylcyclotetrasiloxane(“D₄”), decamethylcyclopentasiloxane (“D₅”), anddodecamethylcyclohexasiloxane (“D₆”) as well as linear or branchedorganopolysiloxanes having the formula:M′D′_(q)T′_(s)M′wherein:

M′ is R¹⁹ ₃SiO_(1/2);

D′ is R²⁰ ₂SiO_(2/2);

T′ is R²¹SiO_(3/2)

R¹⁹, R²⁰ and R²¹ are each independently alkyl, aryl or aralkylcontaining from one to sixty carbon atoms;

q and s are each independently integers from 0 to 300, preferably from 0to 100, more preferably from 0 to 50, and most preferably from 0 to 20.

In a preferred embodiment, the silicone composition of the presentinvention comprises, per 100 parts by weight (“pbw”) of the siliconecomposition, from 0.1 to 99 pbw, more preferably from 0.5 pbw to 30 pbwand still more preferably from 1 to 15 pbw of the polyether siloxanecopolymer network and from 1 pbw to 99.9 pbw, more preferably from 70pbw to 99.5 pbw, and still more preferably from 85 pbw to 99 pbw of thefluid.

The polyether siloxane copolymer network compositions of the presentinvention may be utilized as prepared or as the silicone component inemulsions. As is generally known, emulsions comprise at least twoimmiscible phases one of which is continuous and the other which isdiscontinuous. Further emulsions may be liquids with varying viscositiesor solids. Additionally the particle size of the emulsions may be renderthem microemulsions and when sufficiently small microemulsions may betransparent. Further it is also possible to prepare emulsions ofemulsions and these are generally known as multiple emulsions. Theseemulsions may be:

1) aqueous emulsions where the discontinuous phase comprises water andthe continuous phase comprises the polyether siloxane copolymer networkof the present invention;

2) aqueous emulsions where the discontinuous phase comprises thepolyether siloxane copolymer network of the present invention and thecontinuous phase comprises water;

3) non-aqueous emulsions where the discontinuous phase comprises anon-aqueous hydroxylic solvent and the continuous phase comprises thepolyether siloxane copolymer network of the present invention; and

4) non-aqueous emulsions where the continuous phase comprises anon-aqueous hydroxylic organic solvent and the discontinuous phasecomprises the polyether siloxane copolymer network of the presentinvention.

Non-aqueous emulsions comprising a silicone phase are described in U.S.Pat. No. 6,060,546 and co-pending application U.S. Ser. No. 09/033,788filed Mar. 3, 1998 the disclosures of which are herewith and herebyspecifically incorporated by reference.

As used herein the term “non-aqueous hydroxylic organic compound” meanshydroxyl containing organic compounds exemplified by alcohols, glycols,polyhydric alcohols and polymeric glycols and mixtures thereof that areliquid at room temperature, e.g. about 25° C., and about one atmospherepressure. The non-aqueous organic hydroxylic solvents are selected fromthe group consisting of hydroxyl containing organic compounds comprisingalcohols, glycols, polyhydric alcohols and polymeric glycols andmixtures thereof that are liquid at room temperature, e.g. about 25° C.,and about one atmosphere pressure. Preferably the non-aqueous hydroxylicorganic solvent is selected from the group consisting of ethyleneglycol, ethanol, propyl alcohol, iso-propyl alcohol, propylene glycol,dipropylene glycol, tripropylene glycol, butylene glycol, iso-butyleneglycol, methyl propane diol, glycerin, sorbitol, polyethylene glycol,polypropylene glycol mono alkyl ethers, polyoxyalkylene copolymers andmixtures thereof.

Once the desired form is attained whether as a silicone only phase, ananhydrous mixture comprising the silicone phase, a hydrous mixturecomprising the silicone phase, a water-in-oil emulsion, an oil-in-wateremulsion, or either of the two non-aqueous emulsions or variationsthereon, the resulting material is usually a high viscosity cream withgood feel characteristics, and high absorbance of volatile siloxanes. Itis capable of being blended into formulations for hair care, skin care,antiperspirants, sunscreens, cosmetics, color cosmetics, insectrepellants, vitamin and hormone carriers, fragrance carriers and thelike.

The personal care applications where the polyether siloxane copolymernetwork of the present invention and the silicone compositions derivedtherefrom of the present invention may be employed include, but are notlimited to, deodorants, antiperspirants, antiperspirant/deodorants,shaving products, skin lotions, moisturizers, toners, bath products,cleansing products, hair care products such as shampoos, conditioners,mousses, styling gels, hair sprays, hair dyes, hair color products, hairbleaches, waving products, hair straighteners, manicure products such asnail polish, nail polish remover, nails creams and lotions, cuticlesofteners, protective creams such as sunscreen, insect repellent andanti-aging products, color cosmetics such as lipsticks, foundations,face powders, eye liners, eye shadows, blushes, makeup, mascaras andother personal care formulations where silicone components have beenconventionally added, as well as drug delivery systems for topicalapplication of medicinal compositions that are to be applied to theskin.

In a preferred embodiment, the personal care composition of the presentinvention further comprises one or more personal care ingredients.Suitable personal care ingredients include, for example, emollients,moisturizers, humectants, pigments, including pearlescent pigments suchas, for example, bismuth oxychloride and titanium dioxide coated mica,colorants, fragrances, biocides, preservatives, antioxidants,anti-microbial agents, anti-fungal agents, antiperspirant agents,exfoliants, hormones, enzymes, medicinal compounds, vitamins, salts,electrolytes, alcohols, polyols, absorbing agents for ultravioletradiation, botanical extracts, surfactants, silicone oils, organic oils,waxes, film formers, thickening agents such as, for example, fumedsilica or hydrated silica, particulate fillers, such as for example,talc, kaolin, starch, modified starch, mica, nylon, clays, such as, forexample, bentonite and organo-modified clays.

Suitable personal care compositions are made by combining, in a mannerknown in the art, such as, for example, by mixing, one or more of theabove components with the polyether siloxane copolymer network,preferably in the form of the silicone composition of the presentinvention. Suitable personal care compositions may be in the form of asingle phase or in the form of an emulsion, including oil-in-water,water-in-oil and anhydrous emulsions where the silicone phase may beeither the discontinuous phase or the continuous phase, as well asmultiple emulsions, such as, for example, oil-in water-in-oil emulsionsand water-in-oil-in water-emulsions.

In one useful embodiment, an antiperspirant composition comprises thepolyether siloxane copolymer network of the present invention and one ormore active antiperspirant agents. Suitable antiperspirant agentsinclude, for example, the Category I active antiperspirant ingredientslisted in the U.S. Food and Drug Administration's Oct. 10, 1993Monograph on antiperspirant drug products for over-the-counter humanuse, such as, for example, aluminum halides, aluminum hydroxyhalides,for example, aluminum chlorohydrate, and complexes or mixtures thereofwith zirconyl oxyhalides and zirconyl hydroxyhalides, such as forexample, aluminum-zirconium chlorohydrate, aluminum zirconium glycinecomplexes, such as, for example, aluminum zirconium tetrachlorohydrexgly.

In another useful embodiment, a skin care composition comprises thepolyether siloxane copolymer network, preferably in the form of siliconecomposition of the present invention, and a vehicle, such as, forexample, a silicone oil or an organic oil. The skin care compositionmay, optionally, further include emollients, such as, for example,triglyceride esters, wax esters, alkyl or alkenyl esters of fatty acidsor polyhydric alcohol esters and one or more the known componentsconventionally used in skin care compositions, such as, for example,pigments, vitamins, such as, for example, Vitamin A, Vitamin C andVitamin E, sunscreen or sunblock compounds, such as, for example,titanium dioxide, zinc oxide, oxybenzone, octylmethoxy cinnamate,butylmethoxy dibenzoylm ethane, p-aminobenzoic acid and octyldimethyl-p-aminobenzoic acid.

In another useful embodiment, a color cosmetic composition, such as, forexample, a lipstick, a makeup or a mascara composition comprises thepolyether siloxane copolymer network, preferably in the form of siliconecomposition of the present invention, and a coloring agent, such as apigment, a water soluble dye or a liposoluble dye.

In another useful embodiment, the compositions of the present inventionare utilized in conjunction with fragrant materials. These fragrantmaterials may be fragrant compounds, encapsulated fragrant compounds, orfragrance releasing compounds that either the neat compounds or areencapsulated. Particularly compatible with the compositions of thepresent invention are the fragrance releasing silicon containingcompounds as disclosed in U.S. Pat. Nos. 6,046,156; 6,054,547;6,075,111; 6,077,923; 6,083,901; and 6,153,578; all of which are hereinand herewith specifically incorporated by reference.

The uses of the compositions of the present invention are not restrictedto personal care compositions, other products such as waxes, polishesand textiles treated with the compositions of the present invention arealso contemplated.

Experimental Preparation of Polyether Siloxane Copolymer NetworkCompositions

PREPARATION EXAMPLE 1

494.5 g of a hydride fluid with approximate composition M^(H)D₃₀₀ D^(H)₄M^(H) was mixed with 5.5 g of vinyl cyclohexene oxide, 1500 g ofdecamethyl cyclopentasiloxane (D5), and 0.1 g of a platinumdivinyltetramethyldisiloxane catalyst solution. The result was heated to80° C. After a couple of hours, an additional portion of platinumcatalyst solution was added. The material was heated for a total of 4hours at 80° C. In this way a gel material ExpMJO-07-391 was obtainedwith a solids content of about 26%. 567 g of ExpMJO-07-391 was thenmixed with 1433 g of additional D5. Then the result was passed twicethrough a Gaulin homogenizer at 4500 psi. The result, ExpMJO-07-401 hada solids content of about 7.3% and a viscosity of 24,200 cps. Thismaterial gave a very silky feel when rubbed on the skin.

PREPARATION EXAMPLE 2

300 g of a hydride fluid with approximate composition M^(H)D₃₃₇ D^(H)₁₁₈M^(H) was mixed with 3.94 g of vinyl cyclohexene oxide, 37 g ofGulftene C30+ Alpha Olefin Fraction from Chevron (herein defined when asubstituent as C30+), 1022.8 g of decamethyl cyclopentasiloxane (D5),and 0.1 g of a platinum divinyltetramethyldisiloxane catalyst solution.The result was heated to 80° C. for 8 hours producing ExpMJO-07-433.This material had a solids content of about 25.5%. 587.5 g ofExpMJO-07-433 was then swollen with 1412.5 g of additional D5 and thenpassed through a Gaulin homogenizer at 4500 psi. The result,ExpMJO-07-434, had a solids content of about 7.4% and a viscosity of45,000 cps. It also gave a silky feel when rubbed on the skin.

PREPARATION EXAMPLE 3

300 g of a hydride fluid with approximate composition M_(H) _(1.73)D₃₈₈D^(H) _(6.9)M_(0.27) was mixed with 3.00 g of vinyl cyclohexene oxide, 9g of Gulftene C30+ Alpha Olefin Fraction from Chevron, 936 g ofdecamethyl cyclopentasiloxane (D5), and 0.1 g of a platinumdivinyltetramethyldisiloxane catalyst solution. The result was heated to80° C. for 8 hours producing ExpMJO-07-422. This material had a solidscontent of about 25.7%. 591.4 g of ExpMJO-07-422 was then swollen with1408.6 g of additional D5 and then passed through a Gaulin homogenizerat 4500 psi. The result, ExpMJO-07-437, had a solids content of about7.26% and a viscosity of 39,000 cps.

PREPARATION EXAMPLE 4

300 g of a hydride fluid with approximate composition M^(H) _(1.73)D₃₈₈D^(H) _(6.9)M_(0.27) was mixed with 3.00 g of vinyl cyclohexene oxide, 3g of a C-16/18 Alpha Olefin Fraction, 918 g of decamethylcyclopentasiloxane (D5), and 0.1 g of a platinumdivinyltetramethyldisiloxane catalyst solution. The result was heated to80° C. for 8 hours producing ExpMJO-07-424. This material had a solidscontent of about 25.7%. 591.4 g of ExpMJO-07-424 was then swollen with1408.6 g of additional D5 and then passed through a Gaulin homogenizerat 4500 psi. The result, ExpMJO-07-438, had a solids content of about7.57% and a viscosity of 39,500 cps.

PREPARATION EXAMPLE 5

300 g of a hydride fluid with approximate composition M^(H)D₃₃₇ D^(H)_(11.8)M^(H) was mixed with 4.89 g of vinyl cyclohexene oxide, 26.4 g ofGulftene C30+ Alpha Olefin Fraction from Chevron, 733 g of decamethylcyclopentasiloxane (D5), and 0.08 g of a platinumdivinyltetramethyldisiloxane catalyst solution. The result was heated to80° C. for 6 hours producing ExpMJO-07-464. This material had a solidscontent of about 30.84%. 533 g of ExpMJO-07464 was then swollen with 967g of additional D5 and then passed through a Gaulin homogenizer at 4500psi. The result, ExpMJO-07-465, had a solids content of about 11% and aviscosity of 200,000 cps.

PREPARATION EXAMPLE 6

300 g of a hydride fluid with approximate composition MD₁₀₀ D^(H)_(10.5)M was mixed with 13.53 g of vinyl cyclohexene oxide, 34.84 g ofGulftene C30+ Alpha Olefin Fraction from Chevron, 647 g of decamethylcyclopentasiloxane (D5), and 0.10 g of a platinumdivinyltetramethyldisiloxane catalyst solution. The result was heated to80° C. for 6 hours producing ExpMJO-07-477. This material had a solidscontent of about 35.25%. 533 g of ExpMJO-07-464 was then swollen with947 g of additional D5 and then passed through a Gaulin homogenizer at4500 psi. The result, ExpMJO-07-482, had a solids content of about12.69% and a viscosity of 16,500 cps.

PREPARATION EXAMPLE 7

316.4 g of a hydride fluid with approximate composition M^(H)D₂₀₀ D^(H)_(10.5)M^(H) was mixed with 7.56 g of vinyl cyclohexene oxide 7.00 g of4-allyl-2-methoxy-phenol, 840 g of decamethyl cyclopentasiloxane (D5),and 0.09 g of a platinum divinyltetramethyldisiloxane catalyst solution.The result was heated to 80° C. for 6 hours producing ExpMJO-08-537. 418g of ExpMJO-08-537 was then swollen with 582 g of additional D5 and thenpassed through a Gaulin homogenizer at 8000 psi. The result,ExpMJO-08-540, had a solids content of about 12% and a viscosity of198,000 cps.

PREPARATION EXAMPLE 8

Example Showing Gelation Followed by Hydrosilyation. 300 g of a hydridefluid with approximate composition M^(H)D₃₃₇ D^(H) _(11.8) M^(H) wasmixed with 3.94 g of vinyl cyclohexene oxide, 905.4 g of decamethylcyclopentasiloxane (D5), and 0.1 g of a platinum divinyltetramethyldisiloxane catalyst solution. The result was heated to 80° C. for 4hours with good mixing. A small sample of the gelled reaction mixturewas taken out and analyzed by FTIR. This clearly showed that there wasresidual SiH remaining. Next, a mixture of 30 g of the di isostearicacid ester of trimethylolpropane monoallyl ether, 10 g of D5 and 1 dropof Pt catalyst was added. The result was heated for another 2 hours at80° C. At this end of this time a gel was obtained (Gel E) which had asolids content of 25.1%. FTIR analysis showed that the size of the SiHstretch (ca. 2140 cm-1) had substantially decreased.

PREPARATION EXAMPLE 9

Example Showing Addition of a Concentrated Hydridosiloxane. 300 g of ahydride fluid with approximate composition M^(H) _(1.73)D₃₈₈ D^(H)_(6.9)M_(0.27) was mixed with 3.00 g of vinyl cyclohexene oxide, 4.00 gof 4-allyl-2-methoxy-phenol, 20.8 g of Gulftene C30+ Alpha OlefinFraction from Chevron, 984 g of decamethyl cyclopentasiloxane (D5), and0.1 g of a platinum divinyltetramethyl disiloxane catalyst solution. Theresult was heated to 80° C. for an hour with good mixing. At this point,a mixture of 4 g of a trimethylsilyl stopped methyl hydrogen polsiloxaneand 5 g decamethyl cyclopentasiloxane was added. With 3 minutes, thereaction mixture gelled. Heating was continued for 5 hours in order toensure complete reaction.

PREPARATION EXAMPLE 10

300 g of a hydride fluid with approximate composition M^(H)D₂₀₀ D^(H)_(10.5) M^(H) was mixed with 7.22 g of vinyl cyclohexene oxide, 34.1 gof Gulftene C30+ Alpha Olefin Fraction from Chevron, 796 g of decamethylcyclopentasiloxane (D5), and 0.085 g of a platinumdivinyltetramethyldisiloxane catalyst solution. The result was heated to80° C. for 6 hours producing ExpMJO-07-481. 562 g of ExpMJO-07-481 wasthen swollen with a mixture of 938 g of additional D5 and 1.0 g of a 10%solution of methyl di(hydrogenated tallow)amine in Isopar C and thenpassed through a Gaulin homogenizer at 4500 psi. The result,ExpMJO-07-484, had a solids content of about 11.58% and a viscosity of85,000 cps.

Experimental Preparation of Cosmetic Compositions Using PolyetherSiloxane Copolymer Network Compositions

COSMETIC EXAMPLE 1

Composition wt % wt % A(Control) B(Ex1) Stearyl alcohol 15 15Hydrogenated castor oil 5 5 Isododecane 10 10 SF1202 45 35 Talc 1 1 AlZr Trichlorohydrex Gly 24 24 ExpMJO-07-465 0 10

These antiperspirant sticks were made by heating stearyl alcohol,hydrogenated castor oil, isododecane, SF1202 and ExpMJO-07-465 until thegellants were melted. Al Zr Trichlorohydrex gly was added to the batchat 70° C. and mixed until uniform. Antiperspirants were poured tocontainers at about 60° C. The antiperspirant was evaluated forwhiteness, ability to hold liquid, feel, and hardness of the stick. Thewhiteness was determined by applying antiperspirant onto dark colorvinyl slides to mimic the consumer application methods. Vinyl testslides were air dried for 15 min and the whiteness was determined byappearance. The control antiperspirants showed intense whiteness within5-10 min after application. The antiperspirant B showed whitenessreduction as compared to control. Antiperspirant B also demonstrated asuperior ability to hold cosmetic fluid when using thumb pressure wasapplied to the sticks. It also improved the rigidity and resiliency ofthe stick in this formulation. In addition, it provided lubricious skinfeel with powdery finish. Formulation B also modified thecrystallization of organic gelling agents by providing a better and moreuniform matrix and reducing the growth of stearyl alcoholcrystallization matrix.

COSMETIC EXAMPLE 2

Composition A B(Ex2) wt % wt % Part A Propylene glycol 42.2 42.2Hydroxypropyl cellulose 0.5 0.5 DBS 2 2 Part B 30% Al ZrPentachlorohydrex gly 30 30 in propylene glycol Part C SF1202 10 0ExpMJO-07-465 0 10 SF1555 15 15 40% Dimethicone copolyol in D5 0.3 0.3

These clear antiperspirant sticks were prepared by heating propyleneglycol to 80° C. and slowly sprinkling in hydroxypropyl cellulose(HPC).After the HPC was uniformly dispersed, the mixture was heated up to 130°C. and DBS was added to the batch. The glycol mixture was cooled down to100° C. when a solution of the antiperspirant active was added. Thesilicone phase or part C was separately mixed and heated to 80° C. andthen the glycol phase was slowly introduced to the silicone phase.

The clear antiperspirant B in this invention showed no syneresis andincreased stiffness of the stick compared to control. It gave goodpay-out and smooth uniform deposition of antiperspirant active on theskin when compared to control. Cosmetic Example 3 and 4 A B(Ex3) CD(Ex4) Ingredients Wt % Wt % Wt % Wt % Part A SF1202 21.65 11.65 19.29.9 Isododecane 8.7 8.7 Caprylic/capric 3.6 3.6 Triglyceride Dimethicone9.3 9.3 Phenyl trimethicone 9.3 9.3 Sorbitan oleate 1.5 1.5 1.4 1.4 40%Dimethicone 3.75 3.75 3.5 3.5 copolyol in D5 ExpMJO-07-465 10ExpMJO-07-434 9.3 Part B Iron oxides(red, 2.34 2.34 2.18 2.18 yellow,black) TiO₂ 8.73 8.73 8.11 8.11 10% Dimethicone 6.63 6.63 6.15 6.15copolyol in D5 Part C Deionized water 37.75 37.75 34.98 34.98 Butyleneglycol 5 5 4.65 4.65 Xanthan gum 0.1 0.1 0.1 0.1 C₁₁₋₁₅ Pareth-7 0.250.25 0.23 0.23 Magnesium 0.9 0.9 sulfate Parameter Founda- Founda-Founda- Founda- tion A tion B tion C tion D (Ex3) (Ex4) Degree of —Excellent — Excellent coverage¹ Gloss 3.2 3.2 17.2 11.6 Appearance NA NAWashed Partially washed after 5 away away, the cycles of remaining washoff² foundation showed powdery finish.Note:¹= Degree of coverage was conducted against the control. Formulation Awas the control of formulation B and formulation C was the control offormulation D.²= Formulation C and D was tested for appearance of foundation coated onvinyl slides after 5 cycles of wash off. The wash off resistance methodwas described in ASTM D1913.

The foundations were prepared by mixing part A and part B together atroom temperature until uniform. The emulsion was developed when thewater phase (Part C) was added into the oil phase. The foundationsamples were evaluated for coverage on vinyl slides at 24 micron inthickness. All foundations were evaluated on ease of spreadabilityduring draw down, appearance, degree of coverage and shine. Shine wasdetermined by using gloss meter after 12 hours. In this studyformulation B was evaluated against formulation A(control) andformulation D was evaluated against formulation C(control).

Formulation B gave superior uniform coverage by reducing the appearanceof lines and imperfections on the vinyl slides, and by reducing shineduring initial rub-out. However, both formulation A and B did not showthe difference in gloss after 12 hours. Formulation B imparted aluxurious silky feel with a powdery finish appearance. The foundation Bin this invention had improved stability after one week at roomtemperature compared to the formulation A(control) which showedsyneresis at the same time.

Formulation D gave the similar benefits as described in formulation B.In addition, it also provided wash off resistance which made personalcare products more durable to perspiration or during swimming.Formulation D had an ability to control shine as shown in the resultabove.

COSMETIC EXAMPLE 5 AND 6

These two examples were prepared to illustrate organic compatibility ofsilicone gel in this invention and compared it with the currentelastomer gel with an INCI name of cyclopentasiloxane (and)dimethicone/vinyl dimethicone crosspolymer (SFE839).

COSMETIC EXAMPLE 5

Composition Appearance 25% Petrolatum in SFE839 fluid 25% Petrolatum inExpMJO-07-465 gel

When petrolatum was mixed with SFE839, the formulation lost thestructure and became an opaque fluid mixture. This suggested theincompatibility of petrolatum and SFE839. On the other hand, whenpetrolatum was incorporated into the gel of this invention, the gel hadan ability to maintain product integrity, indicating the compatibilityof this gel and petrolatum.

COSMETIC EXAMPLE 6

Composition Appearance 50% Cetearyl methicone in SFE839 Incompatible 50%Cetearyl methicone in ExpMJO-07-465 Compatible

Cetearyl methicone is a linear alkyl substituted silicone and itprovides moisturization to the formulation by creating an occlusivebarrier on the skin. When this silicone moisturizer was combined withthe new gel, it showed good compatibility whereas the SFE839 did not. Inaddition, the gel according to this invention is easier to blend withcosmetic ingredients in that it does not require the high shear mixer orlengthy mixing time required by SFE839.

COSMETIC EXAMPLE 7

This skin treatment gel was prepared by combining all ingredients listedbelow until uniform at room temperature. The gel was used as deliverysystem for skin treatment and it is suitable for both heat sensitive andnon-heat sensitive active ingredients since it does not require heatingduring manufacturing. The absence of water in this formulation ensuresthe efficacy of vitamin C until used. Composition wt %Polymethylsilsesquioxane(Tospearl2000B) 0.5 Vitamin C 1 Hydrogenatedpolydecene 10 ExpMJO-07-434 88.5

COSMETIC EXAMPLE 8

A lip treatment comprising ingredients below is useful for contouring,durability and moisturization feel. Composition wt % ExpMJO-07-465 89Phenylpropyldimethylsiloxysilicate 10 Nylon-12 1

COSMETIC EXAMPLE 9

Silky body lotion is made by combining part A together and heating to80° C. In a separate vessel, part B is mixed and heated to 75° C. Theemulsion is formed when part A and part B are added together under highshear mixing. This lotion provides light and lubricious skin feel.Composition wt % Part A ExpMJO-07-465 10 Caprylic/capric triglyceride 5C₃₀₋₄₅ Alkyl Dimethicone 5 Glyceryl stearate(and) PEG-100 stearate 4Part B Water q.s. Xanthan gum 0.1 Glycerin 2 Preservatives, color,fragrance 1

COSMETIC EXAMPLES 10-13

Water resistant lotions useful for various personal care products wereprepared by combining part A and part B together at room temperature.The lotions were then applied on glass slides and tested for degree ofwater resistance using the method described in ASTM D1913. The degree ofwash off resistance is the numbers of wash off cycles taken before thelotion was completely washed away. The body lotion B-E with the new gelin this invention showed water resistant benefit as shown below.Composition A B C D E Cosmetic Examples Control 10 11 12 13 wt % wt % wt% wt % wt % Part A Sorbitan oleate 0.6 0.6 0.6 0.6 0.6 10% Dimthiconecopolyol in D5 10 10 10 10 10 SF1202 16 4 4 4 4 ExpMJO-07-401 0 12 0 0 0ExpMJO-07-437 0 0 12 0 0 ExpMJO-07-434 0 0 0 12 0 ExpMJO-07-438 0 0 0 012 Part B Glycerin 1 1 1 1 1 Sodium chloride 1 1 1 1 1 Quaternium-15 0.10.1 0.1 0.1 0.1 Water q.s. q.s. q.s. q.s. q.s. Wash off resistant resultFormulation Cycles of wash off A(control) 5 B 15 C 15 D 15 E 10

COSMETIC EXAMPLE 14

Hair shampoo comprising ingredients below gives a silky feel to hairfibers. This shampoo can be prepared into 2 ways; one is directly addsilicone gel to the shampoo, and the other is pre-blend silicone gelwith at least one surfactant and water until emulsion developed and addsilicone gel emulsion to the shampoo.

This shampoo is made by mixing ingredients as ordered. Compositions wt %Ammonium lauryl sulfate 35 Cocamidopropyl betaine 5 Water 56.6Preservative 0.01 Acrylate/C₁₀₋₃₀ alkyl acrylate crosspolymer 0.8 Sodiumhydroxide adjust to pH 7.5 ExpMJO-07-465 2.5 Citric acid adjust to pH 6

COSMETIC EXAMPLE 15

This hair conditioner for daily use provides softness, lubricity andbody. Composition wt % Deionized water 93 Hydroxyethylcellulose 1.5Silicone gel emulsion 2 Cetrimonium chloride 3 Preservatives, color,fragrance q.s.

COSMETIC EXAMPLE 16

The leave on hair conditioner reduces fly-away and increases body andvolume. Composition wt % ExpMJO-07-465 50 Dimethicone copolyol 5Isododecane 45

COSMETIC EXAMPLE 17

This soft solid antiperspirant contains silicone gel an anti-syneresis,thickening and sensory enhancer. The gel shows excellent organiccompatibility. It is used in combination with an organic thickener toachieve the desired texture and rigidity. Part/Wt Ingredient (%)Cyclopentasiloxane (SF1202) 37.0 Dimethicone (SF96-10) 8.0 C12-15 AlkylBenzoate 8.0 Hydrogenated Castor Oil (mp 70° C.) 7.0 C18-36 AcidTriglyceride 7.0 ExpMJO-07-484 5.0 Talc 3.0 Aluminum ZirconiumTetrachlorohydrex Gly 25.0

COSMETIC EXAMPLE 18

This silicone lipstick contains silicone gel to soften lips. There aretwo silicones, SF1528, and Exp-MJO-07-484, which give a unique softsilky feel. Sunscreens could be added to the formulations for solarprotection. Part/Wt Ingredient (%) Cyclopentasiloxane (and)PEG/PPG-20/15 20.0 Dimethicone (SF1528) ExpMJO-07-484 40.0 C18-36 AcidTriglyceride 5.0 Ozokerite 3.0 Polyethylene 5.0 Isododecane 20.0 D&C RedNo. 7 Ca Lake 7.0

Materials listed as SF______ are commercially available siliconematerials available from GE Silicones, 260 Hudson River Road, WaterfordN.Y. 12188.

These examples are to be construed as exemplary in nature only and arenot intended in any way to limit the appended claims. It is contemplatedthat a person having ordinary skill in the art would be able to produceobvious variations of the subject matter and disclosures hereincontained that would be by reason of such ordinary skill within theliteral or equitable scope of the appended claims.

1. A cosmetic composition comprising the reaction product of:M^(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E)_(i)Q_(j) where M=R¹R²R³SiO_(1/2); M^(H)=R⁴R⁵H SiO_(1/2);M^(E)=R⁶R⁷R^(E)SiO_(1/2); D=R⁸R⁹SiO_(2/2); D^(H)=R¹⁰HSiO_(2/2);D^(E)=R¹¹R^(E)SiO_(2/2); T=R¹²SiO_(3/2); T^(H)=HSiO_(3/2);T^(E)=R^(E)SiO_(3/2); and Q=SiO_(4/2); where R¹, R², R³, R⁸, R⁹ and R¹²are independently monovalent hydrocarbon radicals having from one tosixty carbon atoms; R⁴, R⁵ and R¹⁰ are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms or hydrogen;R⁶, R⁷, R¹¹ are independently monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms or R^(E); each R^(E) is independently amonovalent hydrocarbon radical containing one or more oxirane moietieshaving from one to sixty carbon atoms; the stoichiometric subscripts a,b, c, d, e, f, g, h, i, and j are either zero or positive subject to thefollowing limitations: a+b+c>1; b+e+h>1; c+f+i>1; b+e+h>c+f+i; whereinsaid composition having an original volume may be swollen by a lowmolecular weight silicone fluid from 2 to 1,000 times its originalvolume wherein said cosmetic composition exhibits high stability andresistance to syneresis.
 2. The composition of claim 1 where R^(E) hasthe formula:

where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently selectedfrom the group of hydrogen and monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms, Q_(m) is a di- or trivalent hydrocarbonradical having from one to sixty carbon atoms, Q_(n) is a divalenthydrocarbon radical having from one to sixty carbon atoms with thesubscripts m and n independently zero or one subject to the limitationthat when Qm is trivalent one of R¹³ or R¹⁴ is absent.
 3. Thecomposition of claim 1 where R^(E) is obtained by hydrosilylation of acompound selected from the group consisting of 4-vinyl cyclohexeneoxide, allyl glycidyl ether, limonene oxide, 1,2-epoxy-5-hexene,1,2-epoxy-7-octene, norbornadiene monoepoxide and 1,2-epoxy-9-decene. 4.The composition of claim 2 where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ arehydrogen and m and n are zero.
 5. The composition of claim 3 where R^(E)is 4-vinyl cyclohexene oxide.
 6. The composition of claim 1 where R¹,R², R³, R⁸, R⁹ and R¹² are independently selected from the groupconsisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl,dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl,butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl, C30+ and3,3,3-fluoropropyl.
 7. The composition of claim 2 where R¹, R², R³, R⁸,R⁹ and R¹² are independently selected from the group consisting ofmethyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl,stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.8. The composition of claim 3 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.9. The composition of claim 4 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.10. The composition of claim 5 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.11. A cosmetic composition comprising an aqueous emulsion where thediscontinuous phase comprises water and the continuous phase comprises acomposition comprising the reaction product of:M^(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E)_(i)Q_(j) where M=R¹R²R³SiO_(1/2); M^(H)=R⁴R⁵H SiO_(1/2);M^(E)=R⁶R⁷R^(E)SiO_(1/2); D=R⁸R⁹SiO_(2/2); D^(H)=R¹⁰HSiO_(2/2);D^(E)=R¹¹R^(E)SiO_(2/2); T=R¹²SiO_(3/2); T^(H)=HSiO_(3/2);T^(E)=R^(E)SiO_(3/2); and Q=SiO_(4/2); where R¹, R², R³, R⁸, R⁹ and R¹²are independently monovalent hydrocarbon radicals having from one tosixty carbon atoms; R⁴, R⁵ and R¹⁰ are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms or hydrogen;R⁶, R⁷, R¹¹ are independently monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms or R^(E); each R^(E) is independently amonovalent hydrocarbon radical containing one or more oxirane moietieshaving from one to sixty carbon atoms; the stoichiometric subscripts a,b, c, d, e, f, g, h, i, and j are either zero or positive subject to thefollowing limitations: a+b+c>1; b+e+h>1; c+f+i>1; b+e+h>c+f+i; whereinsaid composition having an original volume may be swollen by a lowmolecular weight silicone fluid from 2 to 1,000 times its originalvolume wherein said cosmetic composition exhibits high stability andresistance to syneresis.
 12. The composition of claim 11 where R^(E) hasthe formula:

where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently selectedfrom the group of hydrogen and monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms, Q_(m) is a di- or trivalent hydrocarbonradical having from one to sixty carbon atoms, Q_(n) is a divalenthydrocarbon radical having from one to sixty carbon atoms with thesubscripts m and n independently zero or one subject to the limitationthat when Qm is trivalent one of R¹³ or R¹⁴ is absent.
 13. Thecomposition of claim 11 where R^(E) is obtained by hydrosilylation of acompound selected from the group consisting of 4-vinyl cyclohexeneoxide, allyl glycidyl ether, limonene oxide, 1,2-epoxy-5-hexene,1,2-epoxy-7-octene, norbornadiene monoepoxide and 1,2-epoxy-9-decene.14. The composition of claim 12 where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸are hydrogen and m and n are zero.
 15. The composition of claim 13 whereR^(E) is 4-vinyl cyclohexene oxide.
 16. The composition of claim 11where R¹, R², R³, R⁸, R⁹ and R¹² are independently selected from thegroup consisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl,dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl,butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl, C30+ and3,3,3-fluoropropyl.
 17. The composition of claim 12 where R¹, R², R³,R⁸, R⁹ and R¹² are independently selected from the group consisting ofmethyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl,stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.18. The composition of claim 13 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.19. The composition of claim 14 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.20. The composition of claim 15 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.21. A cosmetic composition comprising an aqueous emulsion where thecontinuous phase comprises water and the discontinuous phase comprises acomposition comprising the reaction product of:M_(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E)_(i)Q_(j) where M=R¹R²R³SiO_(1/2); M^(H)=R⁴R⁵H SiO_(1/2);M^(E)=R⁶R⁷R^(E)SiO_(1/2); D=R⁸R⁹SiO_(2/2); D^(H)=R¹⁰HSiO_(2/2);D^(E)=R¹¹R^(E)SiO_(2/2); T=R¹²SiO_(3/2); T^(H)=HSiO_(3/2);T^(E)=R^(E)SiO_(3/2); and Q=SiO_(4/2); where R¹, R², R³, R⁸, R⁹ and R¹²are independently monovalent hydrocarbon radicals having from one tosixty carbon atoms; R⁴, R⁵ and R¹⁰ are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms or hydrogen;R⁶, R⁷, R¹¹ are independently monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms or R^(E); each R^(E) is independently amonovalent hydrocarbon radical containing one or more oxirane moietieshaving from one to sixty carbon atoms; the stoichiometric subscripts a,b, c, d, e, f, g, h, i, and j are either zero or positive subject to thefollowing limitations: a+b+c>1; b+e+h>1; c+f+i>1; b+e+h>c+f+i; whereinsaid composition having an original volume may be swollen by a lowmolecular weight silicone fluid from 2 to 1,000 times its originalvolume wherein said cosmetic composition exhibits high stability andresistance to syneresis.
 22. The composition of claim 21 where R^(E) hasthe formula:

where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently selectedfrom the group of hydrogen and monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms, Q_(m) is a di- or trivalent hydrocarbonradical having from one to sixty carbon atoms, Q_(n) is a divalenthydrocarbon radical having from one to sixty carbon atoms with thesubscripts m and n independently zero or one subject to the limitationthat when Qm is trivalent one of R¹³ or R¹⁴ is absent.
 23. Thecomposition of claim 21 where R^(E) is obtained by hydrosilylation of acompound selected from the group consisting of 4-vinyl cyclohexeneoxide, allyl glycidyl ether, limonene oxide, 1,2-epoxy-5-hexene,1,2-epoxy-7-octene, norbornadiene monoepoxide and 1,2-epoxy-9-decene.24. The composition of claim 22 where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸are hydrogen and m and n are zero.
 25. The composition of claim 23 whereR^(E) is 4-vinyl cyclohexene oxide.
 26. The composition of claim 21where R¹, R², R³, R⁸, R⁹ and R¹² are independently selected from thegroup consisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl,dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl,cyanoethyl, butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl,C30+ and 3,3,3-fluoropropyl.
 27. The composition of claim 22 where R¹,R², R³, R⁸, R⁹ and R¹² are independently selected from the groupconsisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl,dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl,butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and3,3,3-fluoropropyl.
 28. The composition of claim 23 where R¹, R², R³,R⁸, R⁹ and R¹² are independently selected from the group consisting ofmethyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl,stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.29. The composition of claim 24 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.30. The composition of claim 25 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.31. A cosmetic composition comprising a non-aqueous emulsion where thediscontinuous phase comprises a non-aqueous hydroxylic solvent and thecontinuous phase comprises a composition comprising the reaction productof:M^(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E)_(i)Q_(j) where M=R¹R²R³SiO_(1/2); M^(H)=R⁴R⁵H SiO_(1/2);M^(E)=R⁶R⁷R^(E)SiO_(1/2); D=R⁸R⁹SiO_(2/2); D^(H)=R¹⁰HSiO_(2/2);D^(E)=R¹¹R^(E)SiO_(2/2); T=R¹²SiO_(3/2); T^(H)=HSiO_(3/2);T^(E)=R^(E)SiO_(3/2); and Q=SiO_(4/2); where R¹, R², R³, R⁸, R⁹ and R¹²are independently monovalent hydrocarbon radicals having from one tosixty carbon atoms; R⁴, R⁵ and R¹⁰ are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms or hydrogen;R⁶, R⁷, R¹¹ are independently monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms or R^(E); each R^(E) is independently amonovalent hydrocarbon radical containing one or more oxirane moietieshaving from one to sixty carbon atoms; the stoichiometric subscripts a,b, c, d, e, f, g, h, i, and j are either zero or positive subject to thefollowing limitations: a+b+c>1; b+e+h>1; c+f+i>1;b+e+h>c+f+i; whereinsaid composition having an original volume may be swollen by a lowmolecular weight silicone fluid from 2 to 1,000 times its originalvolume wherein said cosmetic composition exhibits high stability andresistance to syneresis.
 32. The composition of claim 31 where R^(E) hasthe formula:

where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently selectedfrom the group of hydrogen and monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms, Q_(m) is a di- or trivalent hydrocarbonradical having from one to sixty carbon atoms, Q_(n) is a divalenthydrocarbon radical having from one to sixty carbon atoms with thesubscripts m and n independently zero or one subject to the limitationthat when Qm is trivalent one of R¹³ or R¹⁴ is absent.
 33. Thecomposition of claim 31 where R^(E) is obtained by hydrosilylation of acompound selected from the group consisting of 4-vinyl cyclohexeneoxide, allyl glycidyl ether, limonene oxide, 1,2-epoxy-5-hexene,1,2-epoxy-7-octene, norbornadiene monoepoxide and 1,2-epoxy-9-decene.34. The composition of claim 32 where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸are hydrogen and m and n are zero.
 35. The composition of claim 33 whereR^(E) is 4-vinyl cyclohexene oxide.
 36. The composition of claim 31where R¹, R², R³, R⁸, R⁹ and R¹² are independently selected from thegroup consisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl,dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl,butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl, C30+ and3,3,3-fluoropropyl.
 37. The composition of claim 32 where R¹, R², R³,R⁸, R⁹ and R¹² are independently selected from the group consisting ofmethyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl,stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.38. The composition of claim 33 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.39. The composition of claim 34 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.40. The composition of claim 35 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.41. A cosmetic composition comprising a non-aqueous emulsion where thecontinuous phase comprises a non-aqueous hydroxylic solvent and thediscontinuous phase comprises a composition comprising the reactionproduct of:M_(a)M^(H) _(b)M^(E) _(c)D_(d)D^(H) _(e)D^(E) _(f)T_(g)T^(H) _(h)T^(E)_(i)Q_(j) where M=R¹R²R³SiO_(1/2); M^(H)=R⁴R⁵H SiO_(1/2);M^(E)=R⁶R⁷R^(E)SiO_(1/2); D=R⁸R⁹SiO_(2/2); D^(H)=R¹⁰HSiO_(2/2);D_(E)=R¹¹R^(E)SiO_(2/2); T=R¹²SiO_(3/2); T^(H)=HSiO_(3/2);T^(E)=R^(E)SiO_(3/2); and Q=SiO_(4/2); where R¹, R², R³, R⁸, R⁹ and R¹²are independently monovalent hydrocarbon radicals having from one tosixty carbon atoms; R⁴, R⁵ and R¹⁰ are independently monovalenthydrocarbon radicals having from one to sixty carbon atoms or hydrogen;R⁶, R⁷, R¹¹ are independently monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms or R^(E); each R^(E) is independently amonovalent hydrocarbon radical containing one or more oxirane moietieshaving from one to sixty carbon atoms; the stoichiometric subscripts a,b, c, d, e, f, g, h, i, and j are either zero or positive subject to thefollowing limitations: a+b+c>1; b+e+h>1; c+f+i>1; b+e+h>c+f+i; whereinsaid composition having an original volume may be swollen by a lowmolecular weight silicone fluid from 2 to 1,000 times its originalvolume wherein said cosmetic composition exhibits high stability andresistance to syneresis.
 42. The composition of claim 41 where R^(E) hasthe formula:

where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently selectedfrom the group of hydrogen and monovalent hydrocarbon radicals havingfrom one to sixty carbon atoms, Q_(m) is a di- or trivalent hydrocarbonradical having from one to sixty carbon atoms, Q_(n) is a divalenthydrocarbon radical having from one to sixty carbon atoms with thesubscripts m and n independently zero or one subject to the limitationthat when Qm is trivalent one of R¹³ or R¹⁴ is absent.
 43. Thecomposition of claim 41 where R^(E) is obtained by hydrosilylation of acompound selected from the group consisting of 4-vinyl cyclohexeneoxide, allyl glycidyl ether, limonene oxide, 1,2-epoxy-5-hexene,1,2-epoxy-7-octene, norbornadiene monoepoxide and 1,2-epoxy-9-decene.44. The composition of claim 42 where R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸are hydrogen and m and n are zero.
 45. The composition of claim 43 whereR^(E) is 4-vinyl cyclohexene oxide.
 46. The composition of claim 41where R¹, R², R³, R⁸, R⁹ and R¹² are independently selected from thegroup consisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl,dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl,butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl, C30+ and3,3,3-fluoropropyl.
 47. The composition of claim 42 where R¹, R², R³,R⁸, R⁹ and R¹² are independently selected from the group consisting ofmethyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl,stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.48. The composition of claim 43 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.49. The composition of claim 44 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.50. The composition of claim 45 where R¹, R², R³, R⁸, R⁹ and R¹² areindependently selected from the group consisting of methyl, ethyl,sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl,propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy,2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and 3,3,3-fluoropropyl.51. The cosmetic composition of claim 1 wherein the cosmetic compositionis selected from the group consisting of deodorants, antiperspirants,combination antiperspirant deodorants, shaving products, skin lotions,moisturizers, toners, bath products, cleansing products, hair careproducts, shampoos, conditioners, mousses, styling gels, hair sprays,hair dyes, hair coloring products, hair bleaches, hair waving products,hair straighteners, manicure products nail polish, nail polish remover,nail creams, nail lotions, cuticle softeners, protective creams,sunscreen, insect repellent, anti-aging products, color cosmetics,lipsticks, foundations, face powders, eye liners, eye shadows, blushes,makeup, mascaras, personal care formulations where silicone componentshave been conventionally added, and drug delivery systems for topicalapplication of medicinal compositions that are to be applied to theskin.
 52. The cosmetic composition of claim 11 wherein the cosmeticcomposition is selected from the group consisting of deodorants,antiperspirants, combination antiperspirant deodorants, shavingproducts, skin lotions, moisturizers, toners, bath products, cleansingproducts, hair care products, shampoos, conditioners, mousses, stylinggels, hair sprays, hair dyes, hair coloring products, hair bleaches,hair waving products, hair straighteners, manicure products nail polish,nail polish remover, nail creams, nail lotions, cuticle softeners,protective creams, sunscreen, insect repellent, anti-aging products,color cosmetics, lipsticks, foundations, face powders, eye liners, eyeshadows, blushes, makeup, mascaras, personal care formulations wheresilicone components have been conventionally added, and drug deliverysystems for topical application of medicinal compositions that are to beapplied to the skin.
 53. The cosmetic composition of claim 21 whereinthe cosmetic composition is selected from the group consisting ofdeodorants, antiperspirants, combination antiperspirant deodorants,shaving products, skin lotions, moisturizers, toners, bath products,cleansing products, hair care products, shampoos, conditioners, mousses,styling gels, hair sprays, hair dyes, hair coloring products, hairbleaches, hair waving products, hair straighteners, manicure productsnail polish, nail polish remover, nail creams, nail lotions, cuticlesofteners, protective creams, sunscreen, insect repellent, anti-agingproducts, color cosmetics, lipsticks, foundations, face powders, eyeliners, eye shadows, blushes, makeup, mascaras, personal careformulations where silicone components have been conventionally added,and drug delivery systems for topical application of medicinalcompositions that are to be applied to the skin.
 54. The cosmeticcomposition of claim 31 wherein the cosmetic composition is selectedfrom the group consisting of deodorants, antiperspirants, combinationantiperspirant deodorants, shaving products, skin lotions, moisturizers,toners, bath products, cleansing products, hair care products, shampoos,conditioners, mousses, styling gels, hair sprays, hair dyes, haircoloring products, hair bleaches, hair waving products, hairstraighteners, manicure products nail polish, nail polish remover, nailcreams, nail lotions, cuticle softeners, protective creams, sunscreen,insect repellent, anti-aging products, color cosmetics, lipsticks,foundations, face powders, eye liners, eye shadows, blushes, makeup,mascaras, personal care formulations where silicone components have beenconventionally added, and drug delivery systems for topical applicationof medicinal compositions that are to be applied to the skin.
 55. Thecosmetic composition of claim 41 wherein the cosmetic composition isselected from the group consisting of deodorants, antiperspirants,combination antiperspirant deodorants, shaving products, skin lotions,moisturizers, toners, bath products, cleansing products, hair careproducts, shampoos, conditioners, mousses, styling gels, hair sprays,hair dyes, hair coloring products, hair bleaches, hair waving products,hair straighteners, manicure products nail polish, nail polish remover,nail creams, nail lotions, cuticle softeners, protective creams,sunscreen, insect repellent, anti-aging products, color cosmetics,lipsticks, foundations, face powders, eye liners, eye shadows, blushes,makeup, mascaras, personal care formulations where silicone componentshave been conventionally added, and drug delivery systems for topicalapplication of medicinal compositions that are to be applied to theskin.